Trialkylamine salts of dithiocarbanilic acids



United States atent lice.

TRIALKYLAMINE SAIATS 61F DiTI-IIGCARBANHJIC CIDS Application October 28,1955 Serial No. 543,620

6 Claims. (Cl. 260-01) No Drawing.

The present invention is concerned with tn'alkylamine salts ofdithiocarbanilic. acids of the formula In this and succeeding formulae,R represents a nonacidic homocyclic aromatic radical of the benzeneseries, each A represents an alkyl radical containing from 1 to 3 carbonatoms, inclusive, and B represents an alkyl radical containing from oneto 12 carbon atoms, inclusive. The expression non-acidic homocyclicaromatic radical of the benzene series is defined as inclusive of suchradicals as phenyl, halophenyl, nitrophenyl, alkylphenyl, alkoxyphenyl,dialkylaminophenyl and acylphenyl. In the latter definition, halo refersto bromine, chlorine and iodine and the terms alkyl, alkoxy and acylrefer to radicals containing one and two carbon atoms.

These new compounds are crystalline solids or viscous liquids which aresomewhat soluble in many organic solvents and of low solubility inwater. They are useful as intermediates for the preparation in excellentyields of the isothiocyanates corresponding to the salts of thedithiocarbanilic acids. In such use, substantially equimolecularproportions of the trialkylamine salt of the dithiocarbanilic acid,sodium hydroxide and lead nitrate are mixed and blended together inWater at temperatures of from 20 to 45 C. Following the reaction, thereaction mixture may be steam distilled to separate the correspondingisothiocyanate as a crystalline solid or vis- I cous liquid. The newtrialkylamine salts of the dithiocarbanilic acids also are useful asparasiticides and adapted to be employed as active toxic constituents ofcompositions for the control of insects, bacteria and fungi.

The new trialkylamine salts of the dithiocarbanilic acids may beprepared by reacting together (1) carbon disulfide, (2) a tertiary amineof the formula and (3) an arylamine of the formula R--NH reactionconveniently is carried out in an inert organic solvent in which thedesired trialkylammonium dithiocarbanilate is insoluble, and preferablyin a low boiling solvent such as diethyl ether, isopropyl ether andnpentane. Good results are obtained when substantially equimolecularproportions of the reactants are employed. In a preferred operation,optimum yields are obtained when employing small excesses in the amountof about ten percent each of the tertiary amine and carbon disulfidereagents.

In the foregoing method, the tertiaryamine and arylamine may bedispersed in the reaction solvent and the carbon disulfide addedportionwise thereto. In an alternative procedure, the carbon disulfide,tertiaryamine and arylamine are combined and blended together in the The2,827,483 Patented Mar. 18, 1958 reaction solvent. The reaction isoftentimes somewhat exothermic and takes place smoothly at temperaturesof from 20 to 50 C. The temperature may be controlled by the addition orsubtraction of heat as may be required. In a convenient method ofoperation, the reaction is carried out at the boiling temperature of thereaction mixture and under reflux. During the reaction, the desiredproduct separates in the reaction mixture as a viscous liquid orcrystalline solid. The latter may be separated by decantation orfiltration and thereafter purified by conventional methods.

The following examples illustrate the invention and are not to beconstrued as limiting:

S Omr-h-sqqna-omm 107.2 grams (1 mole) of o-toluidine, 111.3 grams (1.1moles) of tn'ethylamine, 83.8 grams (1.1 moles) of carbon disulfide and500 milliliters of n-pentane were placed in a reactor equipped with astirrer and condenser. With the stirrer operating the mixture was heatedat the boiling temperature. During the heating an oil phase beganseparating in the mixture and started to solidify after about 15minutes. Stirring was thereafter continued and the mixture maintained atthe boiling temperature for about three hours to complete the reaction.The reaction mixture was then filtered to separate a triethylammoniumZ-methyldithiocarbanilate product as a crystalline residue. The latterwas obtained in a yield of 68.6 percent. The product melted at from 72to 76 C. and contained nitrogen and sulfur contents of 9.5 and 22.08percent, respectively, as compared to theoretical contents of 9.85 and22.5 percent.

76.6 grams (0.6 mole) of p-chloroaniline, 50.2 grams (0.66 mole) ofcarbon disulfide, 133.5 grams (1.32 moles) of triethylamine and 500milliliters of diethyl ether were placed in a reactor equipped withstirrer and condenser. With the stirrer operating, the mixture washeated at the boiling temperature. During the heating an oil phase beganseparating in the mixture and started to solidify after about one-halfhour. Stirring was thereafter continued and the mixture maintained atthe boiling temperature for about 3.5 hours and thereafter set aside for16 hours at room temperature to complete the reaction. The reactionmixture was then filtered to separate a triethylammonium4-chlorodithiocarbanilate product as a crystalline solid melting at from82 to 87 C. The latter was obtained in a yield of 68.4 percent and hadsulfur, nitrogen and chlorine contents of 21.15, 9.18 and 11.62 percent,respectively, as compared to theoretical contents of 21.02, 9.19 and11.63 percent.

Example 3.-Triethylamine salt of 3-;1itrodithiocarbanilic acid 138.1grams (1.0 mole) of 3-nitroaniline, 111.3 grams (1.1 moles) oftn'ethylamine, 83.8 grams (1.1 moles) of carbon disulfide and 3 litersof diethyl ether were placed in a flask with agitation and allowed tostand at roorntemperature for-"1 8 hours. An additional 1.1 moles ofeach of triethylamine and carbon disulfide were then added to themixture with agitation and the resulting product set aside for severaldays at room temperature. During the -latter period a triethylammonium3-nitrodithiocarbanilate product precipitated as ;a crystalline solidand was separated by filtration. The separated product amountedto ayield of 44.3 percent. The product melted at from89 to 92 C. andhasSuIfurand-nitrogen contents of 20.4 and 13.1 percent, respectively,as compared to theoretical contents of 20.32 and 13.32

percent. r Example 4.-Triethylamine salt of 3-acetyldithiacarbanilicacid 7 GHQ-i l S V V OnmiLs-rvnQ-omm In a similar manner,m-acetyldithiocarbanilic acid, carbon disulfide and triethylamine werereacted together in diethyl ether'to'obtaina triethylammonium 3-acety1-dithiocarbanilate product in a yield of 78 percent. The product meltedat 77 -80 C. and had sulfur and nitrogen contents of 20.16 and 8.8percent, respectively, as compared to theoretical contents of 20.59 and9.0 percent.

Example 5.Triethylamine salt of 2-metha'xydithi0carbanilic acid 123.2grams (1.0 mole) of o-anisidine, 83.8 grams (1.1 moles) of carbondisulfide, 111.3 grams.(1.1 moles) of triethylamine and 0.5 liter ofdiisopropylether were placed in a flask with agitation and allowed tostand for about three hours at room temperature. During this period atriethylammonium 2-methoxydithiocarbanilate product separated andsolidified as a crystalline solid. The product was recovered byfiltration and found to melt at from 62 to 71 C. The product wasobtained in a yield of 73.6 percent and contained sulfur and nitrogencontents of 20.8 and 9.3 percent, respectively, as

compared to'theoretical contents of 2:34 and 9.33 percent.

Example 6.Triethylamine salt of 5-chl0r0 2-meth0xydithiocarbanilic acidCHa-O Example 7.Tfiethylamine salt of 4-(dimethylamino)- Idithiocarbanilic acid 100 grams (0.734 mole) ofN,N-dimethyl-p-phenylene- V diamine, 61.4 grams (0.807 mole) of carbondisulfide,

81.7 grams (0.807 mole) oftriethylamine and 0.75 liter of diisopropylether were placed in a flask and stirred for about three hours. Duringthis period a triethylammonium 4-(dimethylamino)-dithiocarbanilateproduct precipitated in the mixture as a crystalline; solid and wasseparated by filtration. The product was obtained in a yield of 88.2percent and contained sulfur and nitrogen contents of 19.8 .and 13.29percent, respectively, .as.co1npared to theoretical. contents .ofl0.5and 13-.4percent.

Example 8.--N,N-dimethyl N-dodecylamine salt of dithiocarbanilic acid18.6 grams (0.2 mole) of aniline, 16.8 grams (0.22 mole) of carbondisulfide, 47.0 grams (0.22 mole) of N,N-dimethyl N-dodecylarnine andmilliliters of n-pentane were placed in a flask and agitated for abouttwo hours. During the latter period, the reactionmixture separated intoa solvent layer and an organic oil layer. The latter was separated bydecantation toobtain an N,N-dimethyl N-dodecylammonium-dithiocarbanilateproduct as a viscous liquid in a yield of 77i9 percent. The N,N-dimethylN-dodecylamine salt of dithiocarbanilic acid has a molecular weight of382.

Example 9 atfrom 73.5' to 775 C. and having nitrogen and sulfur contentsof 9.4 and 21.8 percent, respectively.

-An .N,N-diisopropy1 N-hexylammonium 2,4-dimethyldithiocarbanilateproduct by reacting together 2,4-dimethylaniline, carbon disulfide andN,N-dipropyl N- hexylamine. This product has a molecular weight 015382 Atriethylammonium 2,6-dimethyldithiocarbanilate product by reactingtogether 2,6-dimethylaniline, carbon disulfide and triethylamine. Thisproduct was a crystalline solid melting at from 82 to86 Crand havingnitrogen and sulfur contents of 9.36 and 20.8 percent, respectively, ascompared to theoretical contents of 9.39 and 21.48 percent.

A triethylammonium 2,4,S-trimethyldithiocarbanilate product by reactingtogether 2,4,5-trimethylaniline, carbon disulfide and triethylamine.This salt was a .semisolid material having a nitrogen content of-8.71as,compared toa theoretical content of 8.97. a

Example 10 vIn the manner as describedin ExampleL:otherxsaltsl'of vdithiocarbanilic .acids may be prepared as followsi .A trimethylammonium3-iododithiocarbani1ate .product byreacting together m-iodoaniline,carbon disulfide and trimethylar'nine.

This product vhas .a molecular weight of 354.

A tripropylammonium 4-ethyldithiocarbanilate -product byreacting'together .4-.ethylaniline, carbon disulfide and tripropylamine.Thisproduct'has a molecular weight of 340.

A triethylammonium 2-chlorodithiocarbanilate product by reactingtogether o-chloroaniline, carbon disulfide and 'triethylamine. This saltwas a crystalline solid melt-.

ing at from 71 to 78 C. and having nitrogen .and sulfur-contents of 9.36and 20.8, respectively.

-A triethylammonium 3-chlorodithiocarbanilate product by reactingtogether m-chloroaniline, carbon disulfide and triethylamine. This saltwas a crystalline solid melting at from 84 to 87C. and having nitrogenand sulfur contents of 9.02 and 21.63 percent, respectively.

. A triethylarnmonium 4-bromodithiocarbanilate product byreactingtogether p-bromoaniline, carbon disulfide and triethylamine. This saltmelted at from .73 to 78 C. and had nitrogen and sulfur contents of 7.81and 17.54 percent, respectively, as compared to theoretical contents of8.02 and 18.35 percent.

A triethylammonium 3-bromodithiocarbanilate produetbyreacting,togetherm-hromoaniline, carbon disulfide i and triethylamine. This saltmelted at from 70 to 77 C.

A triethylammoniurn 4-iododithic-carbanilate product by reactingtogether 4-iodoani1ine, carbon disulfide and triethylamine. This saltmelted at from 84 to 90 C. and had a sulfur content of 16.3 percent ascompared to a theoretical content of 16.17 percent.

Example 11 In a manner comparable to that described in Example 5, othersalts of dithiocarbanilic acids may be prepared as follows:

An N,N-diethyl N-octylammonium 3-ethoxydithiocarbanilate product havinga molecular weight of 321 by reacting together 3-ethoxyaniline, carbondisulfide and N,N-diethyl N-octylamine.

A trimethylammonium 2,4-dimethoxydithiocarbanilate product having amolecular weight of 288 by reacting together 2,4-dirnethoxyaniline,carbon disulfide and trimethylamine.

Example l2.Triethylamine salt of N-methyZdithiOcarbamic acidTriethylammonium N-methyldithiocarbanilate may be prepared in accordancewith the methods herein disclosed. In a representative operation, 107.2grams (1.0 mole) of N-methylaniline, 83.8 grams (1.1 moles) of carbondisulfide, 111.3 grams (1.1 moles) of triethylarnine and 0.5 liter ofdiisopropyl other were placed in a reactor and the mixture stirred forabout 1.5 hours and thereafter set aside for about 20 hours. During thereaction a triethylammoniurn N-methyldithiocarbanilate productprecipitated in the mixture as a crystalline solid. The latter wasseparated by filtration in a yield of 42.3 percent. The product meltedat 65 67 C. and had sulfur and nitrogen contents of 22.1 and 9.42percent, respectively, as compared to theoretical contents of 22.55 and9.85 percent.

The products of the preceding examples are useful as parasiticides andadapted to be employed in disinfectant and pesticide compositions. Insuch use, the compounds may be employed as constituents of solventsolutions and aqueous dispersions or emulsions, or in mixture with inertfinely divided powders. in a representative operation againstRhizoczonia s0lani and Pusariurn spp. substantially complete controlshave been obtained with compositions containing ten parts by weight oftriethylarnmonium 4-chlorodithiocarbanilate per million parts by Weightof composition.

We claim:

1. A compound selected from the group consisting of triethyl ammoniumN-rnethyl dithiocarbanilate and the compounds of the formula ReferencesCited in the file of this patent FOREIGN PATENTS Great Britain Nov. 11,1941 OTHER REFERENCES Losanitsch: Berichte, vol. 40, p. 2977 (1907).Potts: Chem. Abstracts, vol. 38, p. 2398 (1944).

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No,2,827,483 March 18, 1958 Bryant C, Fischback et aln It is herebycertified that error appears in the printed specification of the abovenumbered patent requiring correction and that the Letters Patent shouldread as corrected below,

Column 3, line 43, for "2034" read 21.34

Signed and sealed this 15th day of July 1958.

(SEAL) Attesting Officer Commissioner of Patents

1. A COMPOUND SELECTED FROM THE GROUP CONSISTING OF TRIETHYL AMMONIUMN-METHYL DITHIOCARBANILATE AND THE COMPOUNDS OF THE FORMULA